Thermoplastic acrylic polymer coated composite structure

ABSTRACT

A process for forming a composite useful as an exterior vehicle part that has the following layers components: 
     a. a layer of a glossy clear acrylic thermoplastic finish bonded firmly to 
     b. a layer of an acrylic thermoplastic pigment containing paint firmly bonded to 
     c. a flexible thermoformable polymeric material that is bonded to 
     d. a thick rigid synthetic resinous substrate; 
     The resulting composite and thermoformable laminate that can be made into the above composite having the layers a.-c. of the above structure also are part of this invention.

This is a division of application Ser. No. 238,100, filed Aug. 30, 1988,now U.S. Pat. No. 4,936,906.

BACKGROUND OF THE INVENTION

This invention is related to a composite and in particular to acomposite structure having an acrylic polymer coating.

Exterior auto and truck parts such as fenders, quarter panels, doors,trim parts bumpers, fender extensions and other molded exterior parts ofmoldable thermoplastic polymers are currently being used because oftheir resistance to permanent deformation on impact and their corrosionresistance. Typical moldable thermoplastic polymers that are being usefor these parts are polypropylene, polyethylene, ABS(acrylonitrile-butadiene-styrene terpolymers), polystyrene, andstyrene-acrylonitrile copolymers. These polymers are easily andeconomically molded into auto and truck parts that are substantiallylighter than currently used sheet metal parts thereby favorablyaffecting the weight and fuel economy of the auto or truck and are noteasily dented or subject to deterioration by corrosion and weatheringand are replacing metal parts of automobiles and trucks. Anotheradvantage of these polymers is that more intricate designs can be madein comparison to sheet metals giving the auto makers increased freedomin design of autos.

To reduce air pollution, automobile and truck manufactures need toreduce the amount of painting in the manufacturing process. It would bedesirable to have a thermoplastic auto or truck part that has a highquality durable and weatherable surface whose color matches the paintedsheet metal used to make the auto or truck and that can attacheddirectly in the assembly process and does not require further priming orpainting. This would eliminate the costly and time consuming paintingprocess for thermoplastic parts with the associated pollution problems.

Thermoforming of a thermoplastic sheet having a painted or decoratedfinish has not been successful with typical exterior acrylic finishesthat are used for automobiles and trucks that provide required goodappearance with durability and weatherablility. In thermoforming of thethermoplastic sheet to form the part, the finish or decorated surfacemust flow with the thermoplastic substrate. Typical automotivethermoplastic acrylic lacquers and thermosetting acrylic enamels arerigid finishes that are impossible to process under thermoformingconditions and crack, distort or degrade. Attempts have been made toreformulate such finishes to flexibilize the finish sufficient forthermoforming but resulted in a finish that is too soft for use as anautomotive or truck finish.

It is an objective of this invention to provide a practical andeconomical process for the preparation of thermoplastic acrylic polymercoated thermoformed parts having an excellent overall appearance and afinish that is durable and weatherable and can be used for the exteriorof automobiles and trucks.

SUMMARY OF THE INVENTION

A process for forming a composite useful as an exterior vehicle bodypart using the following steps:

a. a clear layer of an acrylic thermoplastic polymer coating compositionis applied to a flexible polymeric carrier sheet having a smooth glossysurface; wherein the acrylic polymer has a glass transition temperatureof about 75°-105° C. and comprises polymethyl methacrylate, copolymersof methyl methacrylate or graft copolymers of methyl methacrylate ormixtures thereof in an organic solvent having at least 15% by volume ofhigh boiling solvent;

b. the clear layer is partially dried leaving about 5-15% by weight,based on the weight of the clear layer, of solvent in the layer;

c. a pigmented layer of an acrylic thermoplastic polymer coatingcomposition is applied onto the clear layer wherein the polymer has aglass transition temperature of about 75°-105° C. and comprisespolymethyl methacrylate, copolymers of methyl methacrylate or graftcopolymers of methyl methacrylate or mixtures thereof and pigment in anorganic solvent having at least 15% by volume of high boiling solvent;

d. the pigmented layer is partially dried leaving about 5-15% by weight,based on the weight of the pigmented layer, of solvent in the layer;

e. the flexible polymeric carrier sheet with the clear layer andpigmented layer is laminated with heat and pressure to a flexiblethermoformable polymeric material with the pigmented layer being adheredto the thermoformable polymeric material to form a laminate; wherein onremoval of the carrier sheet, the exterior surface of the clear layersubstantially retains the gloss surface transferred to it from thepolymeric carrier sheet;

f. the polymeric carrier sheet is removed from the laminate;

g. the laminate with the clear layer and pigmented layer thereon isthermoformed to form a three dimensionally shaped preformed laminate;and

h. the flexible polymeric material of the thermoformed laminate isadhered to a rigid synthetic resinous substrate to form a compositeuseful as an exterior vehicle body part.

The resulting composite prepared by the above process and the laminateprepared by the above process in steps a.-e. also are part of thisinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross section of the thermoformed composite.

FIG. 2 shows a cross section of the thermoformable laminate or facesheet.

FIG. 3 shows roller coating of paint onto a polyester film and theformation of the thermoformable laminate or face sheet.

FIG. 4 shows the process for making the composite from the laminate orface sheet.

DETAILED DESCRIPTION OF THE INVENTION

A cross section of the composite is shown in FIG. 1. Layer 1 which isthe exterior layer of the composite is a cured acrylic thermoplasticpolymer clear coating that has a glossy finish of automotive quality andmust have excellent weatherability, scratch and mar resistance and goodgloss retention on weathering. Layer 1 is firmly adhered to paint layer2 which is a pigmented cured acrylic thermoplastic polymer coating ofautomotive quality that must withstand weathering and not crack andfade. The combination of layers 1 and 2 must provide the composite withan automotive quality finish that has excellent gloss, high distinctnessof image, gasoline resistance, abrasion and mar resistance, acidresistance and excellent weatherability including good gloss retention.

Layer 3 is a preferred optional layer or layers of a thin layer of athermoplastic polymer, preferably a chlorinated polyolefin that providesintercoat adhesion of the pigmented thermoplastic acrylic layer 2 tolayer 4 which is a flexible thermoformable polymeric material. Layer 5is a relatively thick rigid synthetic resinous substrate, preferable athermoplastic injection molded polymeric material, to which layer 4 isfirmly adhered.

Preferably, the thermoformed composite made according the process ofthis invention has the following thicknesses for each layer of thecomposite:

1. 10-125 micron thick layer of the glossy clear thermoplastic finishthat is bonded firmly to

2. 5-75 micron thick layer of the thermoplastic pigment containing paintlayer that is firmly bonded to

3. (optional) 1-20 micron thick layer or layers of a thermoplasticpolymer that is firmly bonded to

4. 250-1250 micron thick layer of a flexible thermoformable materialthat is bonded to

5. 500-25,000 micron thick rigid layer of a rigid synthetic resinousmaterial.

In the formation of the composite, a thermoformable laminate or facesheet is first formed. FIG. 2 shows a cross section of the laminate orface sheet. The face sheet is composed of layers 1-4 of the compositebefore being thermoformed. FIG. 2 also shows a coated flexible polymericcarrier sheet A, preferably a polyester film A1 coated with a lowsurface energy polymeric coating A2.

The face sheet without the carrier sheet preferably has the followingthickness for each of the layers used:

1. 10-125 micron thick layer of the glossy clear thermoplastic finishthat is bonded firmly to

2. 5-75 micron thick layer of the thermoplastic pigment containing paintlayer that is firmly bonded to

3. (optional) 1-20 micron thick layer or layers of a thermoplasticpolymer that is firmly bonded to

4. 250-1250 micron thick layer of a flexible thermoformable material.

FIG. 3 shows a process for making the laminate or face sheet. A flexiblepolymeric carrier sheet, 6 preferably a polyester film, typically a"Mylar" 200A polyethylene terephthalate film about 50 microns thick, isfed through a 3 roll roller coater 7 containing a clear coatingcomposition 8 and by reverse roller coating about a 10-125 micron thickcoating (dry basis) is applied. Coating line speeds of about 5-25meters/minute are used. The coated film is then passed through the oven9, preferably having multiple heating zones; typically three heatingzones are used. The first zone is at about 50° C. and the last zone isat about 150° C. Oven drying temperatures and line speed are adjusted sothat the resulting clear layer after drying retains about 5-15% byweight of solvent. A solvent incinerator 10 is used to incineratesolvent fumes from the coating composition. The coated film is thenwound into roll 11. The roller coater 7 is filled with a pigmentedcoating coating composition instead of the clear composition and theprocess is repeated to apply about 5-75 micron thick coating (dry basis)of the pigmented coating or color coat over the clear coat layer on thefilm to form a polyester film having a clear coat layer and a color coatlayer. The color coat layer is dried as above so that the resultingcolor coat layer retains about 5-15% by weight of solvent. Optionally,the color coat layer is coated using the same process with a 1-25 micronthick layer (dry basis) of a size layer of thermoplastic polymericmaterial and dried under conditions such that 5-15% by weight of solventis retained in the clear coat layer and the color coat layer.

The resulting coated polyester film is then laminated to a flexiblethermoformable polymeric sheet material 12 about 250-1250 microns inthickness with the coated side of the polyester film being contactedwith the thermoformable polymeric sheet material. The roll of coatedpolyester film 11 and a roll of the thermoformable polymeric sheetmaterial are fed at a line speed of about 5-20 meters/ minute throughguide rollers 13 and then through two heated nip rollers 14 at atemperature of about 150°-250° C. and using a pressure of about 10-75kg/linear cm. The resulting laminate is passed around chill roll 15 andthe resulting face sheet is wound into roll 16.

To prevent sticking of the color coat layer to the surface of thepolyester film when the roll is wound, it is preferred to coat thesurface of the polyester film not in contact with the clear coat andcolor coat layer with a very thin layer of a low surface energypolymeric coating that has a surface energy of less than 42 dynes/cm andat least 4 dynes/cm less than the polyester film. Preferably, thecoating has a surface energy of about 30-42 dynes/cm and has a dry filmthickness of about 5-25 microns. The coating is applied as above byfilling the coater 7 with the low surface energy coating composition andthen applying the composition and heating as above. A typical lowsurface energy coating composition contains an alkyd resin or an acrylicmodified alkyd resin, vinyl chloride/vinyl acetate/ vinyl alcoholpolymer, crosslinked with a fully alkylated melamine resin. Polyethylenewax or polymethylsiloxane resin are added to adjust surface energy. Anextender pigment such as aluminum silicate pigment is added to adjustroughness and a catalyst such as paratoluene sulfonic acid is added toimprove cure response.

FIG. 4 shows the removal of the polyester film from the face sheet 16which is wound onto a roll 17. A section of the face sheet then isthermoformed into into a shaped structure by placing it in a vacuumformer 18 containing heating lamps 19 and the face sheet is heated toabout 100°-180° C. The sheet is then vacuum formed into a shapedstructure 20 having a painted surface which can be used in an injectionmolding process or in another molding process to form an auto or truckpart. The shaped structure 20 is positioned in a conventional injectionmolding machine 21 in which a thick layer of a thermoplastic resin isinjection molded to form a backing layer about 500-25,000 microns inthickness. The resulting part 22 is useful for autos and trucks and hasa surface that is smooth and glossy, has an excellent distinctness ofimage and good color uniformity and in general meets all therequirements of an automotive finish.

The glossy clear finish and the color coat layer provide the laminatewith an exterior decorative finish that is acceptable for automobilesand trucks. The finish must have the following properties to be usefulas an automotive or truck finish: a gloss measured at 20° of at least 80and measured at 60° of at least 90, a distinctness of image (DOI) of atleast 80, gasoline resistance, cleanability, acid spot resistance,hardness of at least 6 Knoops, chip resistance, impact strength of atleast 20 inch pounds measured at room temperature and at -29° C.,excellent paint adhesion, resistance to water and humidity exposure andexcellent outdoor weatherability.

The following is a description of the test methods used to determine theabove properties. Certain test methods identified below are publiclyavailable standard industry specifications and test methods which areincorporated herein by this reference.

Gloss is measured by specular reflectance of a beam of light at anglesof 20° and 60°. Specular reflectance is measured before the finishedpainted surface is buffed and waxed. A Byk-Mallinckrodt "multigloss" or"single gloss" gloss meters are used for measuring specular gloss of thefinish. These gloss meters give values equivalent to those obtained fromASTM Method D-523-67. The preferred test method is described in GM TestSpecification TM-204-A.

Distinctiveness-of-Image (DOI) is a measurement of the clarity of animage reflected by the finish. DOI is measured from the angle ofreflection of a light beam from a spherical surface. DOI is measured bythe Hunterlab Model No. D47R-6F Doigon Gloss Meter. A test panel isplaced on the instrument sensor and the sharpness of the reflected imageis measured. Details of the DOI test procedure are described in GM TestSpecification TM-204-M.

Gasoline Resistance requires no color change, degradation, tackiness,marring or loss of paint adhesion on plastic parts after a finished partis immersed for ten seconds, ten times, in a specified reference fuelwith a 20 second dry off period between each immersion. Immediatelyafter the tenth immersion, the painted surface is checked and must passThumbnail Hardness according to GM Test Specification TM 55-6.

Cleanability is tested according to GM Test Specification TM 31-11 inwhich the painted plastic part is subjected to ten rubs with cheeseclothsaturated with 9981062 Naphtha or currently used and approved cleaningsolvents. There should be no evidence of staining, discoloration, orsoftening of the painted surface and no evidence of color transfer fromthe test part to the cloth. One rub consists of one forward and backwardmotion.

The Acid Spotting Resistance Test requires the painted part to withstandexposure to 0.1N sulfuric acid for 16 hours without any evidence ofstaining, discoloration, or softening of the paint.

Hardness is measured by a standard Knoop Hardness Test.

Chip resistance is determined by a Gravelometer Test described in SAEJ-400. The painted part as received and after 3 and 6 months Floridaexposure, described below, is tested at -23° C. and must have a minimumrating of 8 as determined by F. B. Gravelometer Rating Chart.

Impact strength of a painted part is tested at room temperature by theGardener Test and by the Rosand Test at -29° C.

Paint Adhesion of a painted part is determined by a standard TapeAdhesion Test described in GM Test Specification TM 55-3. According tothis test, a tape is pressed down over an X-shaped cut in the paint coatand the tape is then removed to test the amount of peeling. The testrequires a minimum of 99% of the paint remaining in the tape test area.

Resistance to Water and Humidity Exposure is measured by several tests.In one test, the finished part is exposed to 96 hours of humidityexposure at 100% relative humidity and 38° C. in a humidity cabinetdefined in GM test specification TM 55-3, and a two-hour water immersiontest at 38° C. according to GM test specification TM 55-12. Theresulting paint panel should show no evidence of blistering whenexamined one minute after removal from the test cabinet and shallwithstand the Paint Adhesion Test described above. The Paint AdhesionTest is performed within one minute after removal from either testcabinet. In a second test, the painted panel should withstand 15 cyclesof the Moisture-Cold Cycle Test defined in GM test specification TM45-61A, without any visible signs of cracking or blistering. After 15cycles, the paint panel is exposed to 96 hours of the humidity exposuredescribed above, followed by the Paint Adhesion Test also describedabove. The panel is expected to pass both tests. The Paint Adhesion Testis performed within one minute after removal from the humidityenvironment. One cycle consists of 24 hours and 100% relative humidityat 38° C., 20 hours at -23° C., and four hours at room temperature.

For outdoor weatherability, painted panels are exposed for 3 years inFlorida facing south in a black box positioned 5° from the horizontal.The painted panels should retain 40% of their original gloss and thereshould be no blistering or fading of the paint.

The finish of the clear and color coat of the laminate must besufficiently flexible at thermoforming temperatures and must havesufficient durability to withstand thermoforming and the molding processwithout embritteling, cracking or otherwise degrading the finish. Thefinish must be thermoplastic and flexible and must retain its gloss andother appearance properties after processing.

The thermoplastic acrylic polymer used in the clear and pigment coatingcompositions has a weight average molecular weight of about50,000-500,000 and has a glass transition temperature of about 75°-105°C.

The glossy clear finish is formed from a clear coating composition. Thecomposition contains about 15-80% by weight film forming binder andcorrespondingly about 85-20% by weight of a liquid carrier. Thecomposition has a solvent carrier and the binder of the composition maybe in solution or in dispersion form. The clear coat must be able towithstand an elongation of about 40-150% at a film thickness of about10-125 microns and thermoforming temperatures.

Typically, an acrylic resin such as polymethyl methacrylate andcopolymers thereof can be used as the binder for the clear coatingcomposition. The term copolymer is used herein to designatemulti-component polymers such as terpolymers, 4 component polymers, 5component polymers and the like. Coating compositions of blends of suchpolymers are disclosed in Zimmt U.S. Pat. No. 3,823,205 issued July 9,1974 which is hereby incorporated by reference.

Typical monomers that can be used with methyl methacrylate to form suchcopolymers are alkyl esters of acrylic acid or methacrylic acid wherethe alkyl group has from 1-18 carbon atoms such as methyl acrylate,ethyl acrylate or methacrylate, propyl acrylate or methacrylate,isopropyl acrylate or methacrylate, various butyl acrylates ormethacrylates, cyclohexyl acrylate or methacrylate, benzyl acrylate ormethacrylate, phenyl acrylate or methacrylate, hexyl, octyl, dodecyl,hexadecyl, or octadecyl acrylates or methacrylates, lauryl acrylate ormethacrylate; other monomers can be used such as acrylonitrile,methacrylonitrile, acrylamide, methacrylamide, styrene, alpha-methylstyrene, vinyl toluene, acrylic acid, methacrylic acid, maleic acid orits anhydride, fumaric acid, crotonic acid, allyl methacrylate oracrylate, allyl acetate, glycidyl methacrylate or acrylate, alkyl aminoalkyl methacrylate or acrylate such t-butyl amino ethyl methacrylate,dimethyl amino ethyl methacrylate, hydroxy alkyl acrylates ormethacrylates such as hydroxyethyl methacrylate, hydroxy ethyl vinylether, hydroxyethyl vinyl sulfide, vinyl pyrrolidone and the like.

Dispersions of polymethyl methacrylate copolymers such as "Lucite"Dispersion Lacquers (LDL) also can be used. Typically useful LDL coatingcompositions are described in U.S. Pat. No. 3,660,537 issued May 2, 1972to Fryd et al which is hereby incorporated by reference.

The above methacrylate compositions and the LDL compositions containfrom about 10-30% by weight, based on the weight of the film formingbinder, of components such as plasticizers, ultraviolet light screeners,ultraviolet light stabilizers, microgels, flow control agents andmixtures of any or all of the above.

Typically useful plasticizers are for example, phthalate esters such asbutylbenzyl phthalate, dibutyl phthalate, 2-ethyl hexylbenzyl phthalate,dicyclohexyl phthalate, dibenzyl phthalate, butylcyclohexyl phthalate,di-2-ethylhexyl ester of hexamethylene diphthalate,di-(methylcyclohexyl)phthalate. One preferred plasticizer of this groupis butylbenzyl phthalate. Other plasticizers that can be used are mixedbenzoic acid and fatty oil acid esters of pentaerythritol,poly(propylene adipate) dibenzoate, diethylene glycol dibenzoate,ethylene qlycol adipate benzoate and neopentyl glycol adipate benzoate.Other useful plasticizers are tetrabutylthiodisuccinate, butylphthalylbutyl glycolate, acetyltributyl citrate, dibenzyl sebacate, tricresylphosphate, toluene ethylsulfonamide.

To improve weatherability of the clear coat about 0.1-5%, by weight,based on the weight of the binder, of an ultraviolet light stabilizer orscreeners or a combination of ultraviolet light stabilizers andscreeners can be added to the clear coating composition. Typicallyuseful ultra-violet light stabilizers and screeners are as follows:

Benzophenones such as hydroxy dodecyloxy benzophenone,2,4-dihydroxybenzophenone, hydroxybenzophenones containing sulfonicgroups and the like.

Triazoles such as 2-phenyl-4-(2',2'-dihydryoxylbenzoyl)-triazoles,substituted benzotriazoles such as hydroxy-phenyltriazoles and the like.

Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine,sulfur containing derivatives of dialyl-4-hydroxy phenyl triazines,hydroxy phenyl-1,3,5-triazine and the like.

Benzoates such as dibenzoate of diphenylol propane, tertiary butylbenzoate of diphenylol propane and the like.

Other ultraviolet light stabilizers that can be used include lower alkylthiomethylene containing phenols, substituted benzenes such as1,3-bis-(2'-hydroxybenzoyl)benzene, metal derivatives of3,5-di-t-butyl-4-hydroxy phenyl propionic acid, asymmetrical oxalicacid, diarylamides, alkylhydroxy-phenyl-thioalkanoic acid ester and thelike.

Particularly useful ultraviolet light stabilizers that can be used arehindered amines of bipiperidyl derivatives such as those in Murayama, etal., U.S. Pat. No. 4,061,616, issued Dec. 6, 1977.

The clear coat can also contain transparent pigments, i.e., pigmentshaving the same or similar refractive index as the binder of the clearcoat and are of a small particle size of about 0.015-50 microns. Typicalpigments that can be used in the clear coat in a pigment to binderweight ratio of about 1/1000 to 10/1000 are inorganic siliceouspigments, such as silica pigments. These pigments have a refractiveindex of about 1.4-1.6.

The color coating composition used herein has as the binder any of theaforementioned binders used in the clear coating composition and alsocan use the same plasticizers and it may be advantageous to useultraviolet stabilizers and/or screeners in composition. The compositioncontains pigments in a pigment to binder weight ratio of about 1/100 to100/100.

Any of the conventional pigments used in coating compositions can beutilized such as the following: metallic oxides, such as titaniumdioxide, zinc oxide, iron oxide and the like, metal hydroxide, metalflakes such as aluminum flake, chromates, such as lead chromate,sulfides, sulfates, carbonates, carbon black, silica, talc, china clay,phthalocyanine blues and greens, organo reds, organo maroons and otherorganic pigments and dyes.

The pigments are formulated into a mill base by mixing the pigments witha dispersing resin which may be the same as the binder of thecomposition or may be another compatible dispersing resin or agent. Thepigment dispersion is formed by conventional means such a sand grinding,ball milling, attritor grinding, two roll milling. The mill base is thenblended with the binder of the composition to form the coatingcomposition.

Clear and color coat layers of the aforementioned methacrylate and LDLcoating compositions will be brittle and crack on storage, duringlamination and thermoforming unless the compositions are formulated withcertain active retarder solvents. Typically, these coating compositionscontain about 15-50% by weight of film forming binder andcorrespondingly about 50-85% by weight of a liquid solvent carrier. Atleast 15% by volume of the liquid solvent carrier is an active retardersolvent or solvents that have a boiling point of about 150°-300° C.

In order to be considered an active retarder solvent, the solvent musttotally dissolve or solubilize the coating when applied to a layer ofthe dried coating. Typically useful active retarder solvents are asfollows: 2,2,4-trimethyl pentanediol-1,3 monisobutyrate having a B.P.(boiling point) of 248°C., 2-ethyl hexanol B.P. 182°-186° C., mixedmethyl esters of succinic, glutaric and adipic acids B.P. 196°-225° C.,ethylene glycol monobutyl ether acetate B.P. 181°-194° C. and diethylphthalate B.P. 295° C.

After the application of the clear coating composition to the polyesterfilm, baking conditions are controlled so that the clear layer is onlypartially cured and that the layer retains about 5-15% by weight solventwhich is mostly active retarder solvent. Similarly, the bakingconditions are controlled after application of the color coatingcomposition so that the color layer retains about 5-15% by weightsolvent which is mostly active retarder solvent.

To determine the amount of solvent in layer, a sample is heated forabout 90 minutes at 105° C. and the weight of the sample is determinedand the percent solvent calculated. The active retarder solvents act asa transient plasticizer which reduces the glass transition temperatureof the layer of the coating and flexibilizes the coating whicheliminates cracking during processing and laminating. Duringthermoforming much of the solvent evaporates but any remaining solventreduces the tendency of the clear coat/color coat finish to crack duringthe final molding step. The high boiling point of the active retardersolvents ensures that any escaping solvent does not pop or blister thefinish. Any residual solvent left in the finish of the resultingcomposite will evaporate under ambient conditions within several days orthe composite may be heated to drive off residual solvent.

The flexible polymeric carrier sheet with the clear layer and thepigmented layer can be laminated directly to the flexible thermoformablepolymeric material to form a laminate. The pigmented layer is placed incontact with the flexible thermoformable material. Often it isconvenient or necessary to apply a thin size layer or several sizelayers to the pigmented layer to improve or enhance adhesion to theflexible material. Typical polymeric materials useful for the size layerare polyalkyl acrylates, polyalkyl methacrylates, vinyl chloridepolymers, polyurethanes, polyimides, chlorinated polyolefins andmixtures of the above.

A chlorinated polyolefin size has been found to be particularly usefulfor adhering to thermoformable polyolefin flexible substrates. Thechlorinated polyolefin size layer is applied to the pigmented layerusing the above described coating procedure. A coating composition of asolution of the chlorinated polyolefin is formed. The coatingcomposition contains about 10-60% by weight of the chlorinatedpolyolefin and correspondingly, about 40-90% by weight of solvent. Anyof the conventional solvents can be used that will dissolve thechlorinated polyolefin such as toluene, xylene, n-methyl pyrrolidone andmixtures thereof. The chlorinated polyolefin preferably is a chlorinatedpolypropylene or chlorinated polyethylene containing up to 50% by weightchlorine and preferably 15-50% by weight chlorine. One preferredchlorinated polypropylene is a propylene/maleic anhydride copolymerchlorinated to a level of about 15-50% by weight chlorine. Oneparticularly preferred chlorinated polypropylene of polypropylene andmaleic acid contains about 18-35% by weight chlorine and has an acid no.of about 15.

Up to about 70% but preferably less than 50% by weight of anotherthermoplastic polymer can be mixed with the chlorinated polyolefin whichunder some conditions improves the adhesion of the color coating.Typical thermoplastic polymers that can be used are ethylene vinylacetate polymers, alkyd resins and acrylic polymers.

The thermoformable flexible layer and the rigid layer of the compositeare prepared from standard automotive grade resins. These resinstypically are compounded from thermoformable resins, synthetic rubbers,additives, antioxidants and pigments. Typical thermoformable resins usedhave a melt flow between 0.5-35 g/10 min.. The following are typicalrubbers that are compounded with the polypropylene resins:ethylene/propylene rubbers or ethylene/propylene/maleate rubbers. Thecompounded resins usually contain pigments such as carbon black, calciumcarbonate, silica, talc and other filler or reinforcing pigments.Colored pigments described above can also be used. The specific formulafor the compounded resins varies according to each supplier but eachcomposition must meet the structural specifications such as flexuralmodulus, tensile strength, elongation, tear strength and hardness andprocess constraints such as melt flow and mold shrinkage.

Particularly useful thermoformable resins used for the flexible layerare polyolefins such as polyethylene, polypropylene,acylonitrile/butadiene/styrene polymers, polystyrene,styrene/acrylonitrile copolymers. The acrylic clear and pigmented layerare relatively rigid and brittle and can be used over semirigidthermoformable resins that should a flexural modulus of about100,000-350,000 psi (pounds per square inch).

The layer of flexible thermoformable polymeric material can be formedinto a 250-1250 micron thick sheet using conventional techniques andequipment such as extrusion techniques and equipment. Resins with meltflow indexes of about 0.5-8.0 g/10 min. can be used but resins with meltflow indexes of about 0.5-2.0 g/10 min. are preferred.

The conditions used to form the flexible sheet are such that a sheetwith a smooth "Class A" surface is formed and the sheet has low internalstresses. Stresses in the flexible sheet are measured by cutting a 4×4inch section of the sheet and laying the section on a flat surface. Theedges and the corners of the section should lie flat for an unstressedfilm.

The resin used to form the rigid layer of the composite is an automotivequality resin having a melt flow of about 0.5-8.0 g/10 min. Preferably,the resin has a melt flow of about 4.0-8.0 g/10 min. Any of theaforementioned resin used for the flexible layer can be used that havethe above properties.

Also, other -resinous materials can be used for the rigid layer such asRIM, reinforced injection molded materials which crosslink on curing. Itis also possible to use sheet molding compounts (SMC) which are commonlyused to make auto and truck parts. Can be used with conventional or SMCpress to form the composite.

Since the surface of the composite of this invention is determined bythe surface of the flexible layer, only the flexible layer need be of ahigh quality resin while the rigid layer of the composite can be of alower quality resin. For example, the rigid layer may contain gelparticles which would not affect the appearance or the structuralintegrity of a resulting part formed from the composite.

The ability to separate the surface characteristics from the resin usedto form the rigid layer of the composite allows for the formation ofgreatly improved parts. For example, fiberglass reinforced or otherfiller reinforced resins can be used for the resin for the rigid layerof the composite and stronger more rigid parts can be made than hasheretofor been possible.

The composite of this invention provides automotive manufacturers withmany advantages over prior art compositions. Adhesion problems withinthe recessed portions of a part are minimized, solvent emissionsassociated with spray painting are eliminated, the need for expensivehangers and jigs to maintain shape of a plastic part during baking of anapplied paint are eliminated and the need for a primer which is requiredwith a conventional paint spraying process also is eliminated.Additionally, the composite has a unique set of characteristics thatmake it superior to conventional injection molded and spray paintedparts.

The following Examples illustrate the invention. All parts andpercentages are on a weight basis unless otherwise indicated andmolecular weights are determined by gel permeation chromatography usingpolymethyl methacrylate as a standard.

EXAMPLE 1

A thermoformed thermoplastic polyolefin (TPO) quarter panel for aPontiac Fiero having an exterior high gloss jet black automotive paintwas formed. A cross section of the the quarter panel is similar to thatshown in FIG. 1.

A low surface energy rough enamel was prepared and coated onto onesurface of a sheet of flexible polyester film onto which the clear andcolor coat layers are to be coated to prevent sticking of the clear andcolor coat to the polyester film when the film is coated. The polyesterfilm is a 50 micron thick high gloss "Mylar" 200A polyetheleneterephthlate film made by E. I. Du Pont de Nemours and Company.

The low surface energy rough enamel composition was prepared as follows:

    ______________________________________                                        Ingredient             Parts by Weight                                        ______________________________________                                        Aluminum Silicate Millbase 34.9                                               Isopropyl alcohol   7.80                                                      Methyl isobutyl ketone                                                                           42.40                                                      Union Carbide "UCAR"                                                                             10.20                                                      Aluminum Silicate Pigment                                                                        26.30                                                      Polyethylene Wax    .60                                                       Acrylic Modified Alkyd                                                                           12.70                                                      resin Solution (57.5%                                                         non volatile solvent)                                                                            100.00                                                     Clear Intermediate         38.3                                               Isopropyl alcohol   9.00                                                      Methyl isobutyl ketone                                                                           56.70                                                      Union Carbide UCAR ® VAGH                                                                    15.10                                                      Acrylic modified alkyd                                                                           19.20                                                      resin solution (57.5% N.V.)                                                   Silicone Solution (60% non volatile solvent)                                                         1.2                                                    Paratoluene sulfonic acid (40% non volatile                                                          4.0                                                    solvent)                                                                      Fully methylated melamine                                                                            6.5                                                    Methyl isobutyl ketone 0.5                                                    85/15 methyl isobutyl ketone/                                                                        14.5                                                   Isopropyl alcohol      100.00                                                 ______________________________________                                    

The aluminum silicate millbase was mixed and ground in a sandmill to afineness of 5-10 microns. The aluminum silicate pigment was EngelhardMinerals and Chemical Company's ASP400 grade, the polyethylene wax wasShamrock Chemicals Corporation's S381-N1 grade and the acrylic modifiedalkyd resin solution was Chempol 13-1501-acrylic made by the FreemanChemical Corporation.

The low surface energy rough enamel coating was applied by reverse rollcoater to the polyester film (illustrated in FIG. 2). The enamel coatingwas cured on the polyester sheet by passing it through a multi-zone airdrying oven having three heating zones spaced apart axially along thelength of the carrier, with each drying zone having a progressivelyhigher temperature. The enamel-coated polyester sheet was passed throughthe heating zones of a line speed of about 30 meters per minute; eachheating zone was about 12 meters long. Temperatures of the three heatingzones were: zone 1: 125° C., Zone 2: 165° C., Zone 3: 200° C. By passingthe enamel coated polyester sheet through the three heating zones,substantially all solvent gases from the low surface energy rough enamelcoat were removed and the coating was cured to produce a dry solventresistant coat of uniform thickness about 10 microns thick. The surfaceenergy of the coating was 40 dynes/cm and the surface energy of thepolyester was 45 dynes/cm.

A clear gloss acrylic coating composition was prepared as follows:

    ______________________________________                                                                          Parts Active                                                Parts by Parts    Retarder                                    Ingredients     Weight   Solvent  Solvent                                     ______________________________________                                        Aromatic controlled                                                                           6.94     6.94     --                                          Mineral Spirits                                                               Diethylene glycol                                                                             5.00     5.00     5.00                                        monobutyl ether                                                               Diethyl phthalate                                                                             2.37     2.37     2.37                                        Acrylic Dispersion Resin                                                                      74.05    44.43    15.55                                       (40% solids of an                                                             acrylic polymer                                                               described in Example 1                                                        of U.S. Pat. No. 3,660,537                                                    Tg = 90° C.)                                                           Coconut oil alkyd                                                                             3.33      .51     --                                          (85% solids coconut                                                           oil/ethylene glycol/                                                          phthalic anhydride)                                                           Butyl benzyl phthalate                                                                        3.37     --       --                                          Polyester plasticizer                                                         (85% solids phthalic                                                          anhydride/ethylene                                                            glycol/benzoic acid)                                                          UV absorber ("Tinuvin"                                                                        .75      --       --                                          900, 2-hydroxy-3,                                                             5-di[1,1-dimethyl-                                                            (benzyl)phenyl]-2H-                                                           benzo-triazole                                                                Hindered amine light                                                                          .75      --       --                                          stabilizer ["Tinuvin"                                                         292, bis(1,2,2,6,6-                                                           pentamethyl-4-piperidinyl)                                                    sebacate]                                                                     Silicone solution                                                                             .20       .15     --                                                          100.17   59.91    22.92                                       ______________________________________                                    

The clear acrylic coating was applied to the polyester sheet oppositethe side coated with the low surface energy rough enamel by reversingthe previously prepared roll and roll coating was applied using the sameprocedure as for the enamel coating, except that the line speed was 7.5meters/min. and the temperatures of the zones were: Zone 1: 38° C., Zone2: 93° C., Zone 3: 150° C.; to obtain a film thickness of 35 microns.The clear acrylic coating was formulated with 38.55% active retardersolvent and the resulting coating after drying when measured after 90minutes bake at 105° C. and was shown to have a weight solids of 91.5%and correspondingly 8.5% by weight solvent. The Tg of the cured acryliccoating is 69° C.

A color coating was formulated as follows:

    ______________________________________                                                                         Parts Active                                                         Parts    Retarder                                     Ingredients    Parts    Solvent  Solvent                                      ______________________________________                                        Acrylic dispersion resin                                                                     62.2     37.57    13.15                                        (described above)                                                             Polyester plasticizer                                                                        2.54      .51     --                                           (described above)                                                             Coconut oil alkyd                                                                            2.54      .52     --                                           (described above)                                                             Butyl benzyl phthalate                                                                       1.14     --       --                                           UV absorber    0.32     --       --                                           (described above)                                                             Hindered amine light                                                                         0.32     --       --                                           stabilizer (described                                                         above)                                                                        Silicone solution                                                                            0.03     --       --                                           Black Pigment dispersion                                                                     30.49    18.29     5.49                                        Total          100.00   56.88    18.64                                        ______________________________________                                    

The black dispersion comprised carbon black pigment in a vehicle ofacrylic dispersion resin and butyl benzyl phthalate.

The color coating was coated onto the dried clear coat of the polyesterfilm as described above and then passed through the three-stage ovendescribed above to dry the color coat. The resulting color coat wasabout 30 microns in thickness. The acrylic color coat was formulatedwith 32.8% and the resulting color coat/clear coat film was shown tohave a weight solids of 90.7% and 9.3% by weight solvent.

A CPO (chlorinated polyolefin) size coating composition for use with aTPO backing sheet was formulated as follows:

    ______________________________________                                        Ingredients             Parts                                                 ______________________________________                                        Xylene                  24.60                                                 Chlorinated polyolefin (CPO) solution                                                                 25.00                                                 (Eastman's CP-343-1 25% solids in xylene                                      of chlorinated polypropylene/maleic acid                                      polymer, Acid No. about 15, chlorine                                          content about 18-23%)                                                         Toluene                 42.50                                                 N-methyl pyrrolidone    1.00                                                  Acrylic Dispersion Resin                                                                              6.90                                                  (60% solids of an acrylic vinyl oxazoline                                     ester polymer described in Example 1 of                                       Miller U.S. Pat. No. 3,844,993)                                               Total                   100.00                                                ______________________________________                                    

The binder of the size coating composition contained about 60% CPO(chlorinated polyolefin) and 40% acrylic resin by weight. The size coatcomposition was coated onto the dried color coat to a dry film thicknessof about 2.5 microns using the reverse roll coater. The threetemperature zones were maintained at the same temperature as used forthe clear and color coats but a carrier speed 30 meters per minute wasused. The resulting clear coat/color coat/size film was shown to have asolids weight percent of 92.9.

The resulting paint coated polyester film was then passed to alaminating operation illustrated in FIG. 3, where the paint coat of thepolyester film was laminated to a 500 micron thick TPO (thermoplasticpolyolefin) backing sheet of RPI E-1000, thermoplastic olefinicelastomer to form a face sheet. RPI E-1000 has a flexural modulus ofapproximately 690 MPa and a melt flow rate of approximately 0.8 g/10minutes. In the laminating operation, the backing and the paint coatedpolyester film carrier were run at a lineal speed of 5 meters perminute, and the laminating drum was operated at a temperature of 177° C.The CPO size coat was heat activated and the paint coat was attached tothe face of the TPO backing sheet during the laminating operation, inwhich the hot steel drum applied a force of about 54 kg/lineal cm toform the face sheet.

The resulting face sheet was then stripped from the polyester film andthermoformed into a complex three-dimension shape to form the plasticquarter panel molding (illustrated in FIG. 4). In the thermoformingprocess, the face sheet was first heated to a temperature of about 121°C. to soften the face sheet. The heated face sheet then was placed overa pressure assist vacuum former buck and a vacuum was drawn against thebuck on the TPO side of the face sheet and 2.1 kg/cm² gauge of airpressure applied on the clear coat side of the laminate to form theheated face sheet into the three dimensional shape of the quarter panel.

The resulting thermoformed laminate was then trimmed to fit in the moldcavity of a plastic injection molding machine (see FIG. 4). A quarterpanel was then formed. An elastomeric thermoplastic alloy molding resinRTA-3263 from Republic Plastics Company, having a flexural modulus ofabout 1725 MPa was used for forming the base of the quarter panel. Theresin was injected into the mold behind the thermoformed laminate fusingthe resin to the TPO base of the laminate to form the quarter panelabout 2.5-3.75 mm thick. The mold was operated at the normal melttemperature for the resin. A quarter panel was formed that is in anintegral plastic composite part with a defect-free paint coat on theexterior surface of the panel.

The quarter panel was tested and the tests demonstrated the usefulnessof the paint coat on the exterior automotive finish. The test resultsindicated that desirable appearance properties, including gloss, wereproduced. Specular reflectance measured 85 at 20° and DOI (Distinctnessof Image) measured 85. Color uniformity was good. The test results alsodemonstrated a desirable combination of durability properties. The testpanel passed tests for gasoline resistance, acid resistance, chipresistance (gravelometer reading of 9) and passed QUV and 96 hourhumidity exposure tests.

EXAMPLE 2

A quarter panel was formed as in Example 1, except the CPO size wasomitted and the black color coat/clear coat finish was laminateddirectly to Borg Warner Cycolac® L 20 mil ABS sheet. The black colorcoat/clear coat ABS laminate was then thermoformed as in Example 1except the sheet was heated to around 140° C. before forming.

The resulting thermoformed laminate was then trimmed to fit in the moldcavity of a plastic injection molding machine. A quarter panel was thenformed by injecting Borg Warner Cycolac® L ABS resin behind thethermoform.

The quarter panel was tested and the tests demonstrated the usefulnessof the paint coat as an exterior automotive finish.

Attempts were made to make a face sheet as in Example 1, except the lowsurface energy enamel was not applied to the backside of the polyestersheet. All attempts were unsuccessful because the clear coat adhered tothe backside of the polyester sheet. This prevented further processingbecause the roll could not be unwound.

EXAMPLE 3

A quarter panel was formed as in Example 2, except the following whitecolor coat and clear coat acrylic coatings were substituted for theblack color coat/clear coat acrylic dispersion coating of Example 2. Theclear coat was prepared as follows:

    ______________________________________                                                                         Parts Active                                                         Parts    Retarder                                     Ingredients    Parts    Solvent  Solvent                                      ______________________________________                                        Xylene         68.55    68.55    --                                           Polymethyl methacrylate                                                                      24.8     14.88    --                                           (40% solids)                                                                  Methyl methacrylate/                                                                         26.2     15.70    --                                           Butyl acrylate                                                                copolymer solution                                                            (85/15 - 40% solids)                                                          Methyl methacrylate/                                                                         5.0       3.00    --                                           Diethyl amino ethyl                                                           methacrylate copolymer                                                        solution (99/1-40% solids)                                                    Coconut oil alkyd                                                                            9.4       1.41    --                                           (85% solids coconut                                                           oil/ethylene glycol/                                                          phthalic anhydride)                                                           Butyl benzyl phthalate                                                                       5.0      --       --                                           Cellulose acetate                                                                            16       12.0     --                                           butyrate solution                                                             (Kodak CAB-381-2-                                                             25% solids)                                                                   Cellulose acetate                                                                            13.33    11.33    --                                           butyrate solution                                                             (Kodak CAB-381-2-                                                             15% solids)                                                                   Diethylphthalate                                                                             31.72    31.72    31.72                                        ______________________________________                                    

The clear coating which contained 25% by volume high boiling activesolvents on total organic solvent was applied to the polyester film asin Example 1 to form a dry film having a thickness of about 45 microns.The clear coat was at 88.5% solids after processing.

A color coating was formulated as follows:

    ______________________________________                                                                Parts    Parts Active                                 Ingredients    Parts    Solvent  Solvent                                      ______________________________________                                        Xylene         65.77    65.77    --                                           Coconut oil alkyd                                                                            6.96     1.04     --                                           (85% solids coconut                                                           oil/ethylene glycol/                                                          phthalic anhydride)                                                           White dispersion                                                                             27.37                                                          Butyl benzyl phthalate                                                                       2.67     --       --                                           Polymethylmethacrylate                                                                       15.82    6.33     --                                           solution (40% solids)                                                         Methyl methacrylate/                                                                         1.67     1.0      --                                           Diethyl amino ethyl                                                           methacrylate copolymer                                                        solution (99/1-40% solids)                                                    Methyl methacrylate/                                                                         19.41    11.65    --                                           Butyl acrylate                                                                copolymer solution                                                            (85/15-40% solids)                                                            Polybutylacrylate                                                                            .18      .09      --                                           solution (50% solids)                                                         Cellulose acetate                                                                            10.24    7.68     --                                           butyrate solution                                                             CAB-381-2 (Kodak Co.)                                                         Cellulose acetate                                                                            9.88     8.40     --                                           butyrate solution                                                             (15% solids)                                                                  Diethylphthalate                                                                             40.00    40.00    40.00                                        ______________________________________                                    

The white pigment dispersion comprised titanium dioxide pigment in avehicle of methyl methacrylate/diethyl aminoethyl methacrylate copolymer(99/1).

The white coating which contained 25% by volume high boiling activesolvents or total organic solvent was applied to the polyester film asin Example 2 to form a dry film having a thickness of about 50 microns.The color coat/clear coat was at 90% solids after processing andcontained 10% solvent.

The white color coat/clear coat on treated polyester film was processedas in Example 2 and a quarter panel was formed that is an integralplastic composite part with a defect-free paint coat on the exteriorsurface of the panel.

The quarter panel was tested as in Example 2. The test results showedthat the finish of the panel had desirable appearance properties,including excellent gloss. Specular reflectance was 85 at 20° and DOIwas 85. Color uniformity was good. The test results also demonstrated adesirable combination of durability properties for the panel finish. Thetest panel passed gasoline resistance, acid resistance, abrasionresistance, impact resistance and QUV and 96 hour humidity exposuretests.

EXAMPLE 4

A series of white color coat/clear coat finishes were made based on DuPont "Elvacite" 2010 polymethyl methacrylate bead polymer.

The clear coats were prepared from the following formulations:

    ______________________________________                                        Ingredient      Clear A  Clear B    Clear C                                   ______________________________________                                        Polymethyl methacrylate                                                                       20       15         15                                        (Elvacite 2010)                                                               Butyl benzyl phthalate                                                                        --        5          5                                        Methyl ethyl ketone                                                                           60       60         60                                        Toluene         20       20         --                                        Mixed methyl esters of                                                                        --       --         20                                        succinic, glutonic                                                            and adipic acids                                                              ______________________________________                                    

The ingredients were mixed at high speed at a temperature of about 55°C. The clear coat was then drawn down on a polyester sheet to a dry filmthickness of 35 microns and baked 4 minutes at 150° C. The weight solidsof clears A, B, and C were 98, 98.5 and 89% respectively. Clear coats Aand B were extremely brittle since these coats only contain 2% and 1.5%solvent. Clear coat C was flexible and contained 11% solvent.

Corresponding white color coats were prepared as follows:

    ______________________________________                                        Ingredient      Color A  Color B    Color C                                   ______________________________________                                        White dispersion                                                                              100      100        100                                       (200 P/B TiO.sub.2,                                                           60% solids)                                                                   Polymethyl methacrylate                                                                        80       55         55                                       ("Elvacite" 2010)                                                             Butyl benzyl phthalate                                                                        --        25         25                                       Methylethylketone                                                                             300      300        300                                       Toluene         220      220        --                                        Mixed methyl esters of                                                                        --       --         220                                       succinic, glutonic                                                            and adipic acids                                                              ______________________________________                                    

The ingredients were mixed at high speed at a temperature of about 55°C. The white color coats were drawn down over the corresponding clearcoats to a dry film thickness of 50 microns and baked 4 minutes at 150°C. The weight solids of the resultant color coat/clear coats were 97.5,97 and 91% respectively.

White color coat/clear coat composition A was very brittle and probablycould not be made on production equipment. However this sample wascarefully laminated and thermoformed. It cracked during lamination andthermoforming.

White color coat/clear coat composition B was less brittle and probablycould be made and laminated in production. This sample was carefullylaminated and thermoformed. Cracking occurred during thermoforming.

White color coat/clear coat composition C was laminated and thermoformedwithout difficulty.

I claim:
 1. A composite useful as an exterior vehicle part comprisingthe following layers of components:a. 10-125 micron thick layer of aglossy clear thermoplastic finish comprising an acrylic thermoplasticpolymer having a glass transition temperature of about 75°-105° C. andcomprises polymethyl methacrylate, copolymers of methyl methacrylate, orgraft copolymers of methyl methacrylate or mixtures thereof bondedfirmly to b. 5-75 micron thick layer of a thermoplastic pigmentcontaining paint layer comprising an acrylic thermoplastic polymerhaving a glass transition temperature of about 75°-105° C. of polymethylmethacrylate, copolymers of methyl methacrylate or graft copolymers ofmethyl methacrylate or mixtures thereof and pigment firmly bonded to c.250-1250 micron thick layer of a flexible thermoformable material thatis bonded to d. 500-25,000 micron thick layer of a rigid syntheticresinous material.
 2. The composite of claim 1 in which the acrylicpolymer in the clear layer and the pigmented layer has a weight averagemolecular weight of about 50,000-500,000.
 3. The composite of claim 2wherein clear layer and the pigmented layer form the exterior surface ofthe composite and have a gloss of at least 80 measured at 20° and adistinctness of image of at least
 80. 4. The composite of claim 3 inwhich the acrylic thermoplastic polymer of the clear layer comprisesabout 70-90% by weight of acrylic polymer and about 10-30% by weight ofcomponents selected from the group consisting of plasticizers,ultraviolet light screeners, ultraviolet light stabilizers, microgel,flow control agent and mixtures of any or all of the
 5. The composite ofclaim 4 in which the acrylic polymer of the clear layer comprises ablend of polymethyl methacrylate and a copolymer of methyl methacrylateand an alkyl acrylate or an alkyl methacrylate other than methylmethacrylate.
 6. The composite of claim 4 in which the acrylic polymerof the clear layer comprises polymethyl methacrylate and a graftcopolymer having a backbone of polymerized monomers of ester of acrylicacid or methacrylic acid and allyl methacrylate or allyl acrylategrafting sites having grafted thereto polymeric segments of alkylacrylate or alkyl methacrylate units.
 7. The composite of claim 3 inwhich the the pigmented layer comprises about 70-90% by weight ofacrylic polymer and about 10-30% by weight of components selected fromthe group consisting of plasticizers, ultraviolet light screeners,ultraviolet light stabilizers, microgel, flow control agent and mixturesof any or all of the above and contains pigment in a pigment to binderratio of about 1/100-100/100 wherein the binder comprises the filmforming constituents of the coating composition.
 8. The composite ofclaim 7 in which the acrylic polymer of the pigmented layer comprises ablend of polymethyl methacrylate and a copolymer of methyl methacrylateand an alkyl acrylate or an alkyl methacrylate other than methylmethacrylate.
 9. The composite of claim 7 in which the acrylic polymerof the pigmented layer comprises polymethyl methacrylate and a graftcopolymer having a backbone of polymerized monomers of ester of acrylicacid or methacrylic acid and allyl methacrylate or allyl acrylategrafting sites having grafted thereto polymeric segments of alkylacrylate or alkyl methacrylate units.
 10. The composite of claim 1having at least one size layer positioned between the pigmented layerand the layer of flexible thermoformable material, wherein the sizelayer is about 1-25 microns thick and is selected from the groupconsisting of polyalkyl acrylates, polyalkyl methacrylates,vinylchloride polymers, polyurethanes, polyimides, chlorinatedpolyolefins and any mixtures thereof.
 11. The composite of claim 10 inwhich the size layer comprises a thermoplastic chlorinated polyolefin.12. The composite of claim 11 in which the size layer of chlorinatedpolyolefin consist essentially of propylene/maleic acid copolymercontaining about 15-50% by weight chlorine.
 13. The composite of claim11 in which the size layer consists essentially of a chlorinatedpolypropylene and maleic anhydride polymer containing about 18-35% byweight chlorine.
 14. The composite of claim 10 in which the size layercomprises a mixture containing at least 30% by weight of chlorinatedpolyolefin containing up to 70% by weight of a thermoplastic polymerselected from the group consisting of ethylene vinyl acetate polymer,alkyd resin, and acrylic polymer.
 15. The composite of claim 1 in whichthe flexible thermoformable polymeric material comprises a polymerhaving a flexural modulus of about 175-2100 MPa and is selected from thegroup consisting of thermoplastic polyolefin, acrylonitrile-butadienestyrene terpolymer, polystyrene and styrene-acrylonitrile copolymer. 16.The composite of claim 15 in which the flexible thermoformable polymericmaterial comprises a polyolefin of polypropylene or polyethylene havinga melt flow of about 0.5-2.0 g/10 min.
 17. The composite of claim 15 inwhich the flexible layer of thermoformable polyolefin comprises anextruded sheet of a compounded mixture of polypropylene, a syntheticelastomeric resin, pigments and additives.
 18. The composite of claim 15in which the flexible thermoformable polymer material comprises a sheetof a acrylonitrile-butadiene-styrene terpolymer.
 19. The composite ofclaim 1 in which the rigid synthetic resinous substrate comprises athermoformable polymeric material having a flexural modulus of about175-2100 MPa and has a melt flow rate of about 0.5-8.0 g/10 min. isselected from the group consisting of thermoplastic polyolefin,acrylonitrile-butadiene-styrene terpolymer, polystyrene andstyrene-acrylonitrile polymer and copolymers thereof.
 20. The compositeof claim 19 in which the rigid synthetic resinous substrate comprisesthermoformable polyolefin of polyethylene or polypropylene.
 21. Thecomposite of claim 20 in which the rigid synthetic resinous substratecomprises a thermoformable polyolefin that has a flexural modulus ofabout 175-2100 MPa and the polyolefin has a melt flow rate of about4.0-8.0 g/10 min.
 22. The composite of claim 19 in which the rigidsynthetic resinous substrate comprises acrylonitrile-butadiene-styreneterpolymer.
 23. A laminate useful for making an exterior vehicle partcomprising the following layers of components:a. 10-125 micron thicklayer of a glossy clear thermoplastic finish comprising an acrylicthermoplastic polymer having a glass transition temperature of about75°-105° C. and comprises polymethyl methacrylate, copolymers of methylmethacrylate or graft copolymers of methyl methacrylate or mixturesthereof bonded firmly to b. 5-75 micron thick layer of a thermoplasticpigment containing paint layer comprising an acrylic thermoplasticpolymer having a glass transition temperature of about 75°-105° C. ofpolymethyl methacrylate, copolymers of methyl methacrylate or graftcopolymers of methyl methacrylate or mixtures thereof and pigment firmlybonded to c. 250-1250 micron thick layer of a flexible thermoformablematerial.